Derivatives of phenolphthalein used in polyurethane preparation

ABSTRACT

NOVEL DERIVATIVES OF PHENOLPHTHALEIN ARE PREPARED BY REACTING THE COMPOUND WITH AMMONIA OR AN AMINE, AND WITH AMMONIA OR AN AMINE, FOLLOWED BY A 1,2-EPOXIDE. SUCH POLYHYDRIC DERIVATIVES OF PHENOLPHTHALEIN ARE USEFUL IN THE PREPARATION OF POLYURETHANE COMPOSITIONS SUCH AS FOAMS, COATINGS AND ELASTOMERS, FOR THE PRODUCTION OF SATURATED ALKYD RESINS, UNSATURATED POLYESTERS, AND AS INTERMEDIATES IN THE PREPARATION OF OTHER POLYMER COMPOSITIONS.

United States Patent Int. (:1. C08g 22/14 US. Cl. 260-25 AQ 5 ClaimsABSTRACT OF THE DISCLQSURE Novel derivatives of phenolphthalein areprepared by reacting the compound with ammonia or an amine, and withammonia or an amine, followed by a 1,2-epoxide. Such polyhydricderivatives of phenolphthalein are useful in the preparation ofpolyurethane compositions such as foams, coatings and elastomers, forthe production of saturated alkyd resins, unsaturated polyesters, and asintermediates in the preparation of other polymer compositions.

This is a continuation-impart of copending application Ser. No. 115,870filed Feb. 16, 1971, now abandoned which is a continuation-in-part ofcopendnig application Ser. No. 694,076, filed Dec. 28, 1967 and nowabandoned.

SUMMARY OF THE INVENTION This invention relates to reaction products ofcompositions having the following formulae:

l l H \0 H H E q/6 R HO H H OH wherein y is a number from 0 to 4; R ishydrogen, hydrocarbyl, hydroXy-substituted hydrocarbyl ormercapto-substituted hydrocarbyl; R is chlorine, bromine or alkyl of 1to 12 carbon atoms, and y is 1 to 4 when R, is chlorine or bromine and yis 1 when R, is alkyl; and R is hydrogen, chlorine, bromine, iodine oralkyl of 1 to 6 carbon atoms.

The foregoing compounds are useful in the preparation of polymercompositions such as polyurethane compositions including polyurethanefoams, coating compositions and polyurethane elastomers; polyesterresins including saturated alkyd resins and unsaturated polyesterresins, and as intermediates in the preparation of other polymercompositions and compounds.

3,7l4fi79 Patented Jan. 3t), 1973 The compounds of the invention can beprepared from phenolphthalein or substituted phenolphthaleins of theformula:

wherein R R and y are as defined hereinbefore. Illustrative examples ofsubstituted phenolphthaleins are as follows, wherein the substit-uentsare numbered in accordance with the notation on the foregoing formula:

4,5,6,7-tetrachlorophenolphthalein,

4,5 ,6,7-tetrabromophenolphthalein,

3 ,3 "-dibromophenolphthalein, 3',3"-dichlorophenolphthalein,3',5,3",5"-tetrabromophenolphthalein,3',5',3,5"tetrachlorophenolphthalein, 3,5,3,5"-tetraiodophenolphthalein,

4,5 ,6,7-tetrachloro-3 ',5 ',3 ,5 "-tetrabr omophenolphthalein,6-methylphenolphthalein, S-propylphenolphthalein,5-dodecylphenolphthalein, S-hexylphenolphthalein,3,3"-dimethylphenolphthalein,

3 ,3"-dihexylphenolphthalein, 5,5"-dibromo-3,3"-dimethylphenolphthalein,

and the like.

The hydrocarbyl groups of the hydroxyalkylation agents used in theinvention generally have 2 to 18 carbon atoms, more usually 2 to 6carbon atoms. The hydrocarbyl radicals represented by R generally have 1to 8 carbon atoms. The alkyl groups represented by R, generally have 1to 12 carbon atoms; the alkyl groups represented by R have 1 to 6 carbonatoms. Typical hydrocarbyl radicals include alkyls such as methyl,ethyl, propyl, isobutyl, amyl, octyl, decyl, dodecyl, octadecyl, andhalogen substituted alkyls such as chloromethyl, trichl-oromethyl,fluoropropyl, bromobutyl, iodopropyl, chlorooctyl, bromododecyl and thelike; alkenyl such as vinyl, allyl, butenyl, hexenyl, octenyl,dodecenyl, and halogen-substituted alkenyls such as trichlorovinyl,2-chloroallyl, 2,3-diflu orobutenyl, 2,3-dichlorododeconyl, and thelike; aryl, al kylaryl and arylalkyl of 6 or 7 to 14 carbon atoms,preferably 6 or 7 to 10 carbon atoms, such as phenyl, naphthyl,anthracyl, benzyl, cresyl, tolyl, xylyl, styryl, and halogen-substitutedaryl radicals such as 4- chlorophenyl, 2,4-dichlorophenyl,4-bromophenyl, l-chloronaphthyl, and the like; and alicyclic radicals of3 to about 12 carbon atoms, preferably 3 to 6 carbon atoms, such ascyclopropyl, cyclopentyl, cyclohexyl, cyclooctyl, cyclododecyl, and thelike.

The succeeding description is directed to phenolphthalein as a startingmaterial, but is it understood that the substituted phenolphthaleins arealso intended.

The compositions of the invention are prepared by reactingphenolphthalein with the compound NH("R followed by reaction with ahydroxyalkylation agent such as a mono oxirane ring compound, analkylene halohydrin or an alkylene carbonate. Monomeric 1,2-epoxideshaving 2 to 18 carbon atoms are preferred. Examples of monoepoxides thatcan be employed are ethylene oxide, propylene oxide, butylene oxide,cyclohexane oxide, 2,3- epoxyhexane, epichlorohydrin, styrene oxide,allyl glycidyl ether, methyl glycidyl ether, butyl glycidyl sulfide,glycidyl methyl sulfone, glycidyl methacrylate, glycidyl allylphthalate, and the like. The preferred mono-epoxides are themono-epoxide-substituted hydrocarbons, the monoepoxy-substituted ethers,sulfides, sulfones and esters wherein the said compounds contain 2 to 18carbon atoms. Minor amounts of diepoxides can also be incorporated intothe compositions. Typical diepoxides are 3,4-epoxy-6-methylcyclohexylmethyl-3,4-epoxy 6 methylcyclohexane carboxylate,dicyclopentadiene dioxide, limonene dioxide, 4,4'-(diglycidyl)diphenylpropane, vinylcyclohexane dioxide. Many other epoxides can beused, but the alkylene oxides containing 2 to 6 carbon atoms aregenerally used.

Catalysts for the reaction of the oxirane ring compounds andphenolphthalein are alkali or alkaline earth hydroxides, primary amines,secondary amines, tertiary amines, or basic alkali salts. These includesodium, potassium, lithium, calcium and barium hydroxides, amines suchas methyl, dimethyl, diethyl, trimethyl, triethyl, tripropyl, dimethylbenzyl, dimethyl hydroxyethyl, dimethyl-Z-hydroxypropyl amines, and thelike, and salts of strong bases and weak acids such as sodium acetate orbenzoate. Combinations of catalysts can be used to excellent advantagein obtaining particular products. For example, an amine catalyst, suchas triethylamine, can be used to add the first two moles of propyleneoxide to the compound, and thereafter hydroxyalkylation can be continuedwith ethylene oxide using as a catalyst an alkali metal hydroxide, suchas sodium hydroxide. In general, the hydroxyalkylation reaction can becarried out at 50 to 250 degrees centigrade. The hydroxyalkylation ispreferably performed at 50 to 150 degrees Centigrade. Solvents aregenerally preferred, for example, 1,2-dioxane, 1,4-dioxane,dimethylformamide and diethylformamide.

Hydroxyalkylation can also be carried out with alkylene halohydrinsusing equivalent amounts of an alkali metal hydroxide to bring about thereaction. Suitable alkylene halohydrins are ethylene chloroorbromohydrins, propylene chloroor bromohydrins, 2,3-butylene chloroorbromohydrins, glyceryl chloroor bromohydrins.

Anther method for hydroxyalkylation is by reaction with alkylenecarbonates such as ethylene carbonate and propylene carbonate, using acatalyst such as sodium or potassium carbonated.

In the preparation of the compounds of the invention, it is generallypreferred that all phenolic hydroxyl groups be reacted. However,products prepared by reaction with a number of units ofhydroxyalkylation agent per mole of phenolic hydroxyl are often desired,since the physical properties of the compounds and the polymers in whichthey are employed can be adjusted by controlling the ether chain length.Also, the hydroxyl number of the compounds can be adjusted bycontrolling the ether chain length. Thus, the length of the ether chaindetermines whether polyurethane foams made with the compounds of theinvention are rigid, semirigid or flexible. Generally, for rigid foams,it is not desired to react more than ten moles of the hydroxyalkylationagent per mole of phenolic hydroxyl. It is often desirable to hold theether chain length to a minimum so that the physical properties of thefoams are maximized. The principal criterion is that the length of theether chain is selected to give the desired balance between theviscosity of the condensation product and the physical properties of thefinished foam. In the production of flexible foams, the required etherchain length is dependent on the molecular weight of the phenol-aldehydeor phenol-ketone condensate, but is usually less than 25 units ofhydroxyalkylation agent per mole of phenolic hydroxyl, and generallydoes not exceed about 100 units p r mole. Th yd o y number 01 the poundsof the invention is generally in the range of 200 to 950 when thecompounds are used for rigid foams, and 30 to 200 when the compounds areused for flexible to semirigid foams.

Ammonia and suitable amines of the formula NH(R are useful including thealiphatic monoamines having 1 to 8 carbon atoms in the aliphaticradicals, such as methylamine, ethylamine, propylamine, isopropylamine,butylamine, amylamine, hexylamine, and cyclohexylamine. Also useful arethe aryl amines such as aniline, alkyl-substituted anilines such aspara-toluidine, ortho-toluidine, xylidene, and the like. Diamines suchas hexamethylene diamine can also be employed. The preferred aminecompounds are the monoalkanola-mines such as those having the formula:

wherein X is oxygen or sulfur and the organic radical R is an alkylgroup having up to 8 carbon atoms. Typical amines for use in preparingthe compounds of the invention are ethanolamine, Z-aminopropanol,3-aminopropanol, Z-aminobutanol, 3-aminobutanol, 4-aminobutanol,mercapto-Z-ethylamine, mercapto-Z-propylamine, and the like.

At least the stoichiometric proportion of the ammonia or the desiredamine is employed to react with the phenolphthalein, but an excess ofammonia or the amine can be employed. The reaction can be conducted at atemperature in the range of 5 to degrees centigrade, preferably 25 to 75degrees centigrade. An inert, liquid diluent, such asdimethylformarnide, diethylformamide, 1,2- dioxane, 1,4-dioxane, and thelike, can be employed, if desired. Atmospheric pressure is usuallyemployed, although superatmospheric pressure or vacuum can be used ifdesired. The reaction time can be varied from one to two minutes up toan hour or more. The phenolphthalein and ammonia or amine react in a 1:1molar ratio to produce the amide derivative.

The amine derivatives are useful as intermediates in the preparation ofpolymer compositions, such as polyurethane foams.

Compounds resulting from the reaction of compounds of Formulae I and IIwith oxyalkylation agents are useful in the preparation of polymercompositions. The oxyalkylation agents can be mono oxirane ringcompounds, alkylene halohydrins and alkylene carbonates of the typeillustrated hereinbefore.

Preparation of polyurethane compositions The reaction product ofcompositions I and II are useful in the preparation of polyurethanecompositions by reaction of the compounds with organic polyisocyanates.Various organic polyisocyanates can be used in preparing thepolyurethane compositions of the invention. Among these isocyanates are2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, and mixturesthereof, and particularly the crude mixtures thereof that arecommercially available. Other typical polyisocyanates includemethylenebis(4-phenylisocyanate), n-hexyl diisocyanate, 1,5-naphthalenediisocyanate, 1,3-cyclopentylene diisocyanate, pphenylene diisocyanate,2,4,6-tolylene triisocyanate, 4,4, 4"-triphenylmethane triisocyanate.Higher isocyanates are provided by the liquid reaction products of (l)diisocyanates and (2) polyols or polyamines, and the like. In addition,isothiocyanates and mixtures of isocyanates can be employed. Alsocontemplated are the many impure or crude polyisocyanates that arecommercially available. Especially preferred for use in the inventionare the polyaryl polyisocyanates having the following generalizedformula:

NCO

wherein The preferred composition of this type is polymethylenepolyphenylisocyanate which is a mixture of compounds having thefollowing generalized formula:

NCO

V l. &/

wherein n has an average value of at least 1 and generally is from 1 to3. Other typical compounds of this type include those wherein the Rgroups are chlorine, bromine, methyl or methoxy, and wherein the valueof X is methyl or phenyl in the generic formula.

Any foaming agent commonly used in the art can be employed. These aregenerally those materials that are capable of liberating gaseousproducts when heated, or when reacted with an isocyanate. Preferably,foaming is accomplished by introducing a low boiling liquid into theresin. The heat of reaction is then sufficient to expand the mixture toa foam stable enough to retain its shape until the resin gels. Suitableliquids are the fluorochlorocarbons boiling in the range of -30 to 50degrees centigrade and mixtures thereof, for example,trichlorofluoromethane, trichlorofluoroethane, difluoromonochloroethane,and difiuorodichloroethane. Also useful are mixtures of thefluorocarbons with chlorocarbons such as methylene chloride. Anotherclass of foaming agents that is suitable for carrying out the foamingreaction at an elevated temperature is a tertiary alcohol in combinationwith a strong concentrated acid catalyst. Examples of tertiary alcoholsinclude tertiary amyl alcohol, tertiary butyl alcohol, and the like.Examples of catalysts include sulfuric acid and aluminum chloride. Otherfoaming agents that can be used include the following: polycarboxylicacids, polycarboxylic acid anhydrides, dimethylol ureas, polymethylolphenols, formic acid and tetrahydroxymethylphosphonium chloride.

If desired, a reaction catalyst can be employed in preparing thepolyurethane compositions of the invention. Generally, but notnecessarily, catalysts are employed to prepare the polyurethane foamshaving densities up to about 6 pounds per cubic foot. For foam productshaving densities of 6 pounds per cubic foot and higher, or when acidphosphorus additives are used, reaction catalysts are generally notneeded. The catalysts employed can be any of the known conventionalcatalysts for isocyanate reactions, such as the tertiary amines. Manysuch compounds are useful in the reaction, but they generally have up to20 carbon atoms. Typical compounds of the trialkylamines aretrimethylamine, triethylamine, diethylenetriamine, tetramethyl butanediamine, and the like. Also suitable are the morpholine compounds suchas N-methyl morpholine, N-acetyl morpholine, 4,4'-dithio morpholine, andthe like, and the tertiary amine compounds have other functional groupssuch as diethyl ethanolamine, methyl diethanolamine, N-diethylaminoacetic acid, methyl aminodipropionic acid, N-methyldipropylenetriamine, dimethyl piperazine, and the like. The preferredamine compounds are triethylamine and tetramethyl guanidine. Otherurethane catalysts are also useful, for example, the antimony compounds,such as antimony caprylate, antimony naphthenate, and antimonouschloride; the tin compounds such as dibutyltin dilaurate, tri-n-octyltinoxide, hexabutylditin, tributyltin phosphate or stannic chloride.

In preparing the polyurethane compositions of this invention, thecomponents are preferably reacted in a ratio sufiicient to provide aboutto percent of isocyanato groups with respect to the total number ofhydroxyl and equivalent groups, e.g., amino, anhydride, and carboxylgroups present in the hydroxy-containing polymeric material (and thefoaming agent, if one is provided). The reaction temperature generallyranges from about 20 to about degrees centigrade, although higher andlower temperatures can be used.

Various additives can be incorporated in the polyurethane composition tomodify the properties thereof. For example, the fire resistance of thecomposition can be further improved by the addition of an antimonycompound. Fillers, such as clay, calcium sulfate or ammonium phosphatecan be added to lower the cost; components, such as dyes, can be addedfor color, and fibrous glass, asbestos, and synthetic fibers can beadded to improve strength characteristics. Surfactants are generallyemployed to control cell structure. Suitable cell controllers are thesilicone-glycol copolymers, such as triethoxy dimethyl polysiloxanecopolymerized with a dimethoxypolvethylene glycol.

Especially useful in combination with the reaction product ofcompositions I and II of the invention in the preparation of polymercompositions are organic phosphorus compounds which are capable ofimparting fire retardance to the polymer compositions. Suitablephosphorus compounds include the neutral and acid phosphorus compoundssuch as those disclosed in US. Pat. No. 3,257,337. The phosphoruscompounds are generally employed in a proportion from about 1 part up toabout 20 parts by weight per 100 parts of the total weight of thehydroxylcontaining components. The preferred amount of phosphoruscompound is from about 2 to about 10 parts by Weight per 100 parts ofthe total weight of the hydroxylcontaining components.

Frequently, it is desired to blend the reaction product of compounds Iand II with one or more additional hydroxyl-containing compounds,especially polymeric materials, to obtain a combination of propertiesresulting from both types of polyhydric compositions. However, thecompounds of the invention should comprise at least about 20 weightpercent of the total hydroxyl-containing components. The auxiliaryhydroxyl-containing polymeric materials generally have a hydroxyl numberbetween about 25 and 950 and are polyesters, polyethers, and mixturesthereof. The polyesters are the reaction products of a polyhydricalcohol and a polycarboxylic compound, said polycarboxylic compoundbeing either a polycarboxylic acid, a polycarboxylic acid anhydride, apolycarboxylic acid ester, a polycarboxylic acid halide, or mixturesthereof. The carboxylic compounds can be aliphatic, cycloaliphatic,aromatic, or heterocyclic and either saturated or unsaturated. Among thepolycarboxylic compounds which can be used to form the polyester aremaleic acid, fumaric acid, phthalic acid, isophthalic acid, terephthalicacid, tetrachlorophthalic acid, aliphatic acids such as oxalic, malonic,succinic, glutaric and adipic, 1,4- cyclohexadiene-1,2-dicarboxylicacid, and the like. Additional polycarboxylic compounds which can beused to form the polyester are Diels-Alder adducts ofhexahalocyclopentadiene and a polycarboxylic compound containingaliphatic carbon-to-carbon unsaturation, wherein the halogen is selectedfrom the group consisting of chlorine, bromine, fluorine, and mixturesthereof, for example,

l,4,5,6,7,7-hexachlorobicyclo-(2.2. l )-5-heptene-2,3-

dicarboxylic acid,

1,4,5 ,6-tetrachlor0-7,7-difiuorobicyclo- 2.2. l )-5-heptene-2,3-dicarboxylic acid,

1,4,5 ,6,7,7-hexabromobicyclo- (2.2. l )-5-heptene-2,3-

dicarboxylic acid,

1,4,5 ,6-tetrabromo-7,7-difiuorobicyclo-( 2.2.1 )-5-heptene-2,3-dicarboxylic acid,

and the corresponding acid anhydrides, acid halides and acid esters.Mixtures of any of the above polycarboxylic compounds can be employed.

At least a portion of the total polyhydric alcohol component shouldcomprise a polyhydric alcohol containing at least three hydroxyl groupswhen rigid foams are desired. Where a very rigid structure is desired,the entire alcohol component can comprise a trifunctional alcohol suchas glycerol. Where a less rigid foam product is desired. a difunctionalpolyhydric alcohol such as ethylene glycol or 1,4-butanediol can beutilized as part of the polyhydric alcohol component. Suitablepolyfunctional alcohols include diethylene glycol, propylene glycol,polypropylene glycols, polybutylene glycols, glycerol, hexanetriol,trimethylolpropane, trimethylolethane, mannitol,cyclohexanediol-1,4-glycerol monoethyl ether and the like. The ratio ofthe polyhydric alcohol such as glycerol to the polybasic acid can beexpressed as the hydroxylcarboxyl ratio, which can be defined as thenumber of moles of hydroxyl groups to the number of moles of carboxylgroups in a given weight of resin. This ratio can be varied over a Widerange. Generally, however, a hydroxylcarboxyl ratio of between 1.511 to:1 is needed.

The polyethers employed are known in the art, and are the reactionproducts of (1) either a polyhydric alcohol. a polycarboxylic acid or apolyphenolic compound, and (2) a monomeric 1,2-epoxide possessing asingle 1,2-epoxy group, such as, for example, propylene oxide. Thepolyhydric alcohols, polycarboxylic acids and epoxides which can beemployed are any of the polyhydric alcohols, polycarboxylic acids andepoxides listed hereinbefore. Polyphenolic compounds which can beemployed are the reaction products of phenolic compounds with aldehydes,such as phenol-formaldehyde Novolac resins.

The following resin formulations are typical hydroxylcontainingpolymeric materials that can be used as auxiliary components in thepolyurethane compositions of this invention:

RESIN A 1,4,5,6,7,7-hexachlorobicyclo-(2.2.1)-5-heptene-2,3-

dicarboxylic acid moles 6 Trimethylolpropane do 12 Acid number Hydroxylnumber 365 RESIN B Adipic acid moles 6 Trimethylolpropane do 10 Acidnumber 1 Hydroxyl number 504 RESIN C Polypropylene glycol. Molecularweight ca. 2000 Hydroxyl number 56 RESIN D Adipic acid moles 3 Glyceroldo 5 Acid number 1 Hydroxyl number 640 RESIN E Trimethylolpropane moles1 Propylene oxide do 6 Hydroxyl number 392 RESIN F Trimethylolpropanemoles 8.8 Adipic acid do 5 Phthalic anhydride do 1 Acid number 1Hydroxyl number 435 Preparation of polyester resins The hydroxylcontaining reaction product of compounds of Formulas l and II are usefulin the preparation of saturated polyester resins, i.e., alkyd resins,and unsaturated polyester resins. The hydroxyl-containing compound ofthe invention, either alone or in admixture with other polyhydriccompounds, is reacted with a polycarboxylic compound, such as apolycarboxylic acid, polycarboxylic anhydride, polycarboxylic acidhalide or polycarboxylic acid ester.

The saturated polycarboxylic compounds useful in the preparation ofeither the saturated or unsaturated polyesters can be aliphatic,cycloaliphatic, aromatic or heterocyclic. Illustrative of thesepolycarboxylic acids, acid anhydrides, acid halides and acid esters arephthalic, isophthalic, terephthalic, tetrachlorophthalic, adipic,succinic, and mixtures thereof. Suitable unsaturated polycarboxylicacids having aliphatic carbon-to-carbon double bonds, and thecorresponding acid halides, esters and anhydrides include maleic,chloromaleic, ethylmaleic, itaconic, citraconic, zeronic,pyrochinchoninic and acetylene diearboxylic, either alone or inmixtures.

Suitable saturated polyhydric alcohols for use in combination with thepolyhydric compounds of the invention include ethylene glycol,diethylene glycol, propylene glycol, dipropylene glycol, butane diol,pentane diol, hexane diol, glycerol, mannitol, sorbitol, bisphenols,substituted bisphenols, hydrogenated bisphenols and mixtures thereof.Unsaturated polyhydric alcohols can also be used in combination with thehydroxyl-containing compounds of the invention and the preparation ofpolyester resins. Suitable compounds include butene diol, pentene diol,the unsaturated hydroxy ethers such as allyl or vinyl, glycerol ethers,diol or allyl pentaerythritol ethers and the like.

The properties of polyesters can be varied by using mixtures of thevarious types of acids and alcohols. Also it is possible to render thepolyester compositions fire retardant by the incorporation therein ofsuitable halogencontaining compounds such as the Diels-Alder adducts ofhexahalocyclopentadiene and a polycarboxylic compound containingaliphatic carbon-to-carbon unsaturation, such as those disclosedhereinbefore with respect to the preparation of polyurethanecompositions. Tetrachlorophthalic anhydride and tetrabromophthalicanhydride can also be usefully employed.

The temperature for the reaction between polyhydric alcohols andpolybasic acids ranges from about to 200 degrees centigrade, althoughhigher and lower temperatures can be employed. Esterification catalystssuch as para-toluene sulfonic acid, benzene sulfonic acid,betanaphthylene 'sulfonic acid and the like, or amines such as pyridine,triethyl amine, quinoline and the like can be added to the reactionmixture. The proportion of polyhydric alcohols is approximatelycontrolled by the total low proportion of acids in the esterificationreaction mixture. It is preferred to react the polyhydric alcohols andpolybasic acids in roughly equimolar proportion, however, either theacids or alcohols can be used in substantial excess, if it is desired toform a low molecular polyester resin.

The unsaturated polyester resins of the invention can be cured orcross-linked with a variety of ethylenically unsaturated monomers. Thevinylidene monomers useful in curing the thermoplastic unsaturatedpolymers include vinylic compounds or mixtures thereof capable ofcrosslinking ethylenically unsaturated polymer chains at their points ofunsaturation. Usually they contain the reactive groups H C=C Specificexamples include styrene, chlorostyrenes, methyl styrenes such as alphamethyl styrene, p-methyl styrene, divinyl benzene, indene, unsaturatedesters such as: methyl methacrylate, methyl acrylate, allyl acetate,diallyl phthalate, diallyl succinate, diallyl adipate, diallyl sebacate,diethylene glycol bis (allyl carbonate), triallyl phosphate and otherallyl esters,

and vinyl toluene, diallyl chlorendate, diallyl tetrachlorophthalate,the lower aliphatic esters other than methyl of methacrylic and acrylicacids, ethylene glycol diacrylate, dimethacrylate, diethacrylate, etc.The monomer may be admixed in the polymer in an amount sufficient toproduce a thermoset polymer and the admixture heated to an elevatedtemperature in the presence of a suitable catalyst to cross-link or curethe polymer. With proper catalyst systems, such as cobalt naphthenateand methylethyl ketone peroxide, room temperature cures are obtained.

The proportion of olefinic cross-linking agent to unsaturated polyestercan be varied within the ultimate limits of each without departing fromthe scope of the invention, necessary to produce as infusible,insoluble, polyester resin. In general, the concentration of theunsaturated polyester in the olefinic cross-linking agent can varybetween about ten and ninety percent. Polymerization catalysts arepreferably added to the mixture of unsaturated polyester and olefiniccross-linking agent to effect setting or curing. Catalysts such asbenzoyl peroxide, acetyl peroxide, lauryl peroxide, methylethyl ketoneperoxide, cumene hydroperoxide, and the like, are satisfactory. Suchcatalyst are used in proportions of 0.01 to ten percent of the totalresin, depending on the efficiency of their action and whether or notsubstances which inhibit polymerization are present in the mixture. Thepolymerization reaction can also be hastened by adding promoters such asmetals or metal salts, cobalt resinates, cobalt maleate, cobaltnaphthenate and the like, or amines such as dibutylamine, or mercaptanssuch as dodecyl mercaptan. These are used in proportions similar, orsmaller to, those stated for the catalysts.

The polyester resins of the invention can be used in the preparation ofcoatings of various types, laminates, castings and moldings. Variousadditives can be incorporated in the polyester resins, such as antimonycompounds such as antimony oxide, to render them more fire retardant.Fillers such as clay, calcium sulfate or ammonium phosphate, fibrousglass, asbestos, synthetic fibers, pigments and dyes can also be used asadditives.

The following examples illustrate the various aspects of the inventionbut are not intended to limit it. When no otherwise specified,temperatures are given in degrees centigrade, and parts are by weight.

EXAMPLE 1 291.4 parts by weight of phenolphthalein and 150 parts byweight of dimethyl formamide were charged to a reaction vessel.Thereafter, 17 parts by weight of ammonia were introduced to the reactorbeneath the surface of the reaction mixture at a temperature of about 35to 40 degrees centigrade. The resulting product was a bright red,viscous liquid.

444 parts by weight of the thus-produced compound in solution indimethylformamide were introduced to a heated autoclave. The temperaturewas adjusted to 67 degrees centigrade and ethylene oxide was introducedto the autoclave at such a rate that a pressure of 45 to 60 pounds persquare inch gauge was maintained. During the course of the reaction, thetemperature of the reaction mixture rose to 139 degrees centigrade.After the addition of 376 parts by weight of ethylene oxide, thetemperature of the reaction mixture was decreased to 95 degreescentigrade. The dimethyl formamide was vacuum distilled at 160 degreescentigrade and 1 millimeter of mercury absolute pressure for one-halfhour. There were produced 656 parts by weight of a clear, amber-coloredresin having a molecular weight of 351, a nitrogen content of 2.18Weight percent, a hydroxyl number of 230. The resin was substantiallyfree of phenolic hydroxyl groups as determined by analysis for nitrogencontent and hydroxyl number (calculated nitrogen content: 2.14 weightpercent, calculated hydroxyl number: 252).

EXAMPLE 2 75 parts by weight of phenolphthalein and 600 parts by weightof a 30 Weight percent aqueous solution of ammonium hydroxide werecharged to an autoclave and heated to 170 degrees centigrade at 390pounds per square inch gauge for approximately 1.5 hours. The reactortemperature was allowed to cool gradually. The reactor contents weredischarged to a distillation apparatus and the unreacted ammonia wasdistilled from the reaction product at 80 degrees centigrade, under amoderate vacuum. During the distillation, a dark resinous materialprecipitated from solution. The precipitate was removed from the aqueousphase and dried to yield 53 parts by weight of a brown, brittle solidproduct. The product of the reaction had a melting point of 153-158degrees centigrade, a nitrogen content of 4.52 weight percent andcontained 10.65 weight percent phenolic hydroxyl (calculated nitrogencontent: 4.4 weight percent, calculated phenolic hydroxyl 10.7 weightpercent).

316 parts by weight of the thus produced compound and 200 parts byweight of dimethylformamide were charged into a reaction vessel equippedwith an agitator, thermometer, condenser and gas inlet tube. The mixturewas heated to 160 degrees centigrade. Then propylene oxide wasintroduced as a vapor beneath the surface of the liquid until 196 partsby weight had been added. After the reaction was complete, thedimethylformamide solvent was evaporated from the reaction mixture undervacuum to produce an amber colored resin.

EXAMPLE 3 A polyurethane foam was produced by first blending 100 partsby weight of the product of Example 2, 35 parts by weight oftrichlorofiuoromethane, 0.5 part by weight of the cell controllerprepared in accordance with the disclosure of US Pat. No. 2,824,748 and1 part by weight of triethylamine catalyst. The foregoing blend ofcomponents was mixed with parts by weight of polymethylenepolyphenylisocyanate with vigorous agitation and dispensed into a mold.The resulting polyurethane foam wascured and found to have a density of2.3 pounds per cubic foot, a compressive yield of 23.4 pounds per squareinch and to undergo a 28 percent increase n volume on exposure to apercent relative humidity environment for one week at 70 degreescentigrade.

The polyurethane foams produced from the compounds of the invention havegood physical properties such as mechanical properties, e.g.,compressive strength and the like, good thermal properties, e.g., lowweight and volume change on exposure to dry and humid heat, and good 5percent volume expansion temperature, and good fire retardingcharacteristics. Thus, it is found that the mere addition of a smallproportion of a phosphorus compound renders polyurethane foams made withcompounds of the invention (non-burning) when tested in accordance withASTM test D1692.

EXAMPLE 4 To the resin of Example 2 were added 146 parts by weight ofadipic acid and 1.5 parts by weight of paratoluene sulfonic acid. Thetemperature of the reaction mixture was raised to degrees centigrade,during which time 27 parts by weight of water were removed from thereaction mixture. The resulting polyester resin was recovered and usedto draw thin, flexible films.

While this invention has been described with reference to certainspecific embodiments, it will be recognized by those skilled in the artthat many variations are possible without departing from the spirit andscope of the invention.

1 1 1 2 What is claimed is: (C) a compound selected from the groupconsist- 1. A polyurethane product which comprises the reacing of a monooxirane ring compound, an alkyltion product of components comprising enehalohydrin and an alkylene carbonate, (I) the reaction product of (A) acomposition of the wherein the reaction of (C) with the reactionformula: 5 product of (A) and (B) is carried out at 50 1 0 250 degreescentigrade and II (II) an organic polyisocyanate, said polyisocyanalebeing present in a proportion sufiicient to provide 85 to 115 percent ofreactive isocyanato groups with re- (R J 0 spect to the total number ofhydroxyl and other active hydrogen-containing groups present in said re-5 action product (I). H 2. A polyurethane product in accordance withclaim 1 R5 R which comprises the cellular reaction product of com- HO HH 0H ponents comprising (I), (II) and a ioaming agent.

R R 3. The product of claim 2 wherein (C) is an alkylene 5 5 oxide of 2to 6 carbon atoms, R is hydrogen and y is wherein y is a number from 0to 4, R is selected from the group consisting of chlorine, bromine andThe Pmduct of Clam} 3 Whcfein is 3111111031?!- alkyl of 1 to 12 carbonatoms, and y is 1 to 4 When The/Product of Clam? 2 wherein is ethylene Ris chlorine or bromine and y is 1 when R, is alkyl oxld, 5 hydrogen andy 15 Zeroand R is selected from the group consisting of hydrogen,chlorine, bromine, iodine and alkyl of 1 to 6 carbon atoms; and Japanesepatent specification (publication No. 39/ 24,721

( NH(R2)2 wherein R is selected from the group consisting DONALD E.CZAJA, Primary Examiner of hydrogen, hydrocarbyl, hydroxy-substituted Ihydrocarbyl and mercapto-substituted hydro- WELSH Asslstmt Exammercarbyl wherein the reaction is conducted at a US CL temperature in therange of 5 to degrees centigrade, with 26037 N, 45.75 R, 77.5 AQ

References Cited Po-ww UNITED STATES PATENT OFFICE a v CERTIFICATE OFCORRECTION Patent No. q n7q D t Januarv 30. 1973 Inventor(s) Bruce N.Wilson et al.

It is certified that error appears in the above-identified patent andthat said Letters Patent are hereby corrected as shown below:

Column 5,' .line 15, that portion of the formula reading should readSigned and sealed this 18th day of June 19714..

(SEAL) Att'sst:

EDWARD H.FLETCHER,JR. c. MARSHALL 1mm Attesting Officer Commissioner ofPatents

